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Inorganics
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Organophosphorus Chemistry 2016
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Organophosphorus Chemistry 2016

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (1 December 2016) | Viewed by 38705

Special Issue Editor

Dr. Lee J. Higham

E-Mail Website
Guest Editor
School of Chemistry, Bedson Building, Newcastle University, Newcastle upon Tyne NE1 7RU, UK
Interests: air-stable primary phosphines; asymmetric catalysis with chiral phosphines; fluorescent phosphines for cell imaging and phosphorus-containing materials

Special Issue Information

Dear Colleagues,

Organophosphorus chemistry continues to delight and inspire its many advocates, with the breadth of the subject stretching from fundamental studies into gaining an understanding of the bonding and reactivity of phosphorus compounds, all the way through to the myriad of important applications in a range of fields, including catalysis, agricultural control, biomedicine, and materials science. The range of oxidation states and coordination number in these compounds provides the creative phosphorus chemist with a diverse palette of structural type to investigate, which includes many significant classes, such as the phosphine oxides, phosphonates, phosphoranes, phosphonium salts, chiral phosphines, and the exotic phosphaalkynes/phosphalkenes, in addition to the upsurge of interest in the activation of elemental phosphorus itself. Fascinating breakthroughs continue to be made in all these areas and more, and this Special Issue seeks to highlight some of the most recent and exciting developments.

Dr. Lee J. Higham
Guest Editor

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Keywords

  • Low Coordinate Phosphorus Compounds
  • Chiral Phosphines
  • Elemental Phosphorus
  • Phosphorus-based Materials

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Published Papers (7 papers)

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Research

4123 KiB  
Article
P-Fluorous Phosphines as Electron-Poor/Fluorous Hybrid Functional Ligands for Precious Metal Catalysts: Synthesis of Rh(I), Ir(I), Pt(II), and Au(I) Complexes Bearing P-Fluorous Phosphine Ligands
by Shin-ichi Kawaguchi, Yuta Saga, Yuki Sato, Yoshiaki Minamida, Akihiro Nomoto and Akiya Ogawa
Inorganics 2017, 5(1), 5; https://doi.org/10.3390/inorganics5010005 - 12 Jan 2017
Cited by 4 | Viewed by 5460
Abstract
P-Fluorous phosphine (R2PRf), in which the perfluoroalkyl group is directly bonded to the phosphorus atom, is a promising ligand because it has a hybrid functionality, i.e., electron-poor and fluorous ligands. However, examples of P-fluorous phosphine–metal complexes are [...] Read more.
P-Fluorous phosphine (R2PRf), in which the perfluoroalkyl group is directly bonded to the phosphorus atom, is a promising ligand because it has a hybrid functionality, i.e., electron-poor and fluorous ligands. However, examples of P-fluorous phosphine–metal complexes are still rare, most probably because the P-fluorous group is believed to decrease the coordination ability of the phosphines dramatically. In contrast, however, we have succeeded in synthesizing a series of P-fluorous phosphine–coordinated metal complexes such as rhodium, iridium, platinum, and gold. Furthermore, the electronic properties of R2PnC10F21 are investigated by X-ray analysis of PtCl2(Ph2PnC10F21)2 and the infrared CO stretching frequency of RhCl(CO)(R2PnC10F21)2. IrCl(CO)(Ph2PnC10F21)2- and AuCl(R2PnC10F21)-catalyzed reactions are also demonstrated. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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2407 KiB  
Article
Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium
by Alexander Koch, Sven Krieck, Helmar Görls and Matthias Westerhausen
Inorganics 2016, 4(4), 39; https://doi.org/10.3390/inorganics4040039 - 1 Dec 2016
Cited by 9 | Viewed by 6640
Abstract
Arylmagnesium and -calcium reagents are easily accessible; however, ether degradation processes limit storability, especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with [...] Read more.
Arylmagnesium and -calcium reagents are easily accessible; however, ether degradation processes limit storability, especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofuran yields [Mg{C6H3-2,6-(CH2PPh2)2}2] (2) after recrystallization from 1,2-dimethoxyethane. However, the similarly performed reduction of bromo- (1a) and iodo-2,6-bis(diphenylphosphanylmethyl)benzene (1b) with calcium leads to ether cleavage and subsequent degradation products. α-Deprotonation of tetrahydrofuran (THF) yields 1,3-bis(diphenylphosphanylmethyl)benzene. Furthermore, the insoluble THF adducts of dimeric calcium diphenylphosphinate halides, [(thf)3Ca(X)(µ-O2PPh2)]2 [X = Br (3a), I (3b)], precipitate verifying ether decomposition and cleavage of P–C bonds. Ether adducts of calcium halides (such as [(dme)2(thf)CaBr2] (4)) form, supporting the initial Grignard reaction and a subsequent Schlenk-type dismutation reaction. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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1844 KiB  
Article
PP-Rotation, P-Inversion and Metathesis in Diphosphines Studied by DFT Calculations: Comments on Some Literature Conflicts
by Adam D. Molloy, Goar Sánchez-Sanz and Declan G. Gilheany
Inorganics 2016, 4(4), 36; https://doi.org/10.3390/inorganics4040036 - 18 Nov 2016
Cited by 5 | Viewed by 3951
Abstract
The potential energy surface for internal rotation about the phosphorus–phosphorus bond was calculated at the PCMDCM/B3LYP/6-311++G(d,p) computational level for a set of eight symmetrical, unsymmetrical and P-stereogenic diphosphines; H4P2, Me4P2, (CF3 [...] Read more.
The potential energy surface for internal rotation about the phosphorus–phosphorus bond was calculated at the PCMDCM/B3LYP/6-311++G(d,p) computational level for a set of eight symmetrical, unsymmetrical and P-stereogenic diphosphines; H4P2, Me4P2, (CF3)4P2, Ph4P2, Me2P–P(CF3)2, Me2P–PPh2, and the meso- and dl-isomers of Me(CF3)P–PMe(CF3) and MePhP–PMePh. Certain trends in the data were elucidated and compared with conflicting data from the literature regarding the relative population of anti and gauche rotational isomers. The pyramidal inversion barriers (stereomutation barriers in P-stereogenic cases) for the same set of diphosphines was estimated through the inversion transition states and also compared to literature values. Finally, the Me4P2 + (CF3)4P2 → 2Me2(CF3)2P2 metathesis reaction was also explored to evaluate its feasibility versus inversion. The finding of larger barriers in the metathesis than in the inversion rules in favour of an inversion mechanism for the stereomutation of P-stereogenic diphosphines. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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981 KiB  
Communication
Metal-Free Reduction of Phosphine Oxides Using Polymethylhydrosiloxane
by Emmanuel Nicolas, Antonella Guerriero, Volodymyr Lyaskovskyy, Maurizio Peruzzini, Koop Lammertsma, Luca Gonsalvi and J. Chris Slootweg
Inorganics 2016, 4(4), 34; https://doi.org/10.3390/inorganics4040034 - 3 Nov 2016
Cited by 9 | Viewed by 7041
Abstract
A simple protocol is presented here for the use of inexpensive polymethylhydrosiloxane (PMHS), a waste product of the silicon industry, as stoichiometric reducing agent for phosphine oxides to phosphines, a highly desirable reaction to recover P-based ligands from their spent form. The reactions [...] Read more.
A simple protocol is presented here for the use of inexpensive polymethylhydrosiloxane (PMHS), a waste product of the silicon industry, as stoichiometric reducing agent for phosphine oxides to phosphines, a highly desirable reaction to recover P-based ligands from their spent form. The reactions were studied by screening parameters, such as substrate to reductant ratio, temperature and reaction time, achieving good conversions and selectivities. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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1156 KiB  
Article
η1:η2-P-Pyrazolylphosphaalkene Complexes of Ruthenium(0)
by Victoria K. Greenacre and Ian R. Crossley
Inorganics 2016, 4(4), 30; https://doi.org/10.3390/inorganics4040030 - 30 Sep 2016
Cited by 1 | Viewed by 4254
Abstract
An extended range of novel ruthenium phosphaalkene complexes of the type [Ru{η1-N:η2-P,C-P(pz′)=CH(SiMe2R)}(CO)(PPh3)2] (R = Tol, C6H4CF3-p; pz′ = pz [...] Read more.
An extended range of novel ruthenium phosphaalkene complexes of the type [Ru{η1-N:η2-P,C-P(pz′)=CH(SiMe2R)}(CO)(PPh3)2] (R = Tol, C6H4CF3-p; pz′ = pzMe2, pzCF3, pzMe,CF3; R = Me, C6H4CF3-p; pz′ = pzPh) have been prepared from the respective ruthenaphosphaalkenyls [Ru{P=CH(SiMe2R)}Cl(CO)(PPh3)2] upon treatment with Lipz′. Where R = C6H4CF3-p and pz′ = pzMe2 the complex is characterized by single crystal X-ray diffraction, only the second example of such species being structurally characterized. This indicates enhanced pyramidalisation of the alkenic carbon center when compared with precedent data (R = Me, pz′ = pz) implying an enhanced Ru→π*PC contribution, which can be correlated with the greater donor power of pzMe2. This is similarly reflected in spectroscopic data that reveal significant influence of the pyrazolyl substituents upon the phosphaalkene, stronger donors imparting significantly enhanced shielding to phosphorus; in contrast, a much lesser influence if noted for the silyl substituents. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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914 KiB  
Communication
Zirconium-Catalyzed Alkene Hydrophosphination and Dehydrocoupling with an Air-Stable, Fluorescent Primary Phosphine
by Christine A. Bange, Neil T. Mucha, Morgan E. Cousins, Abigail C. Gehsmann, Anna Singer, Taylor Truax, Lee J. Higham and Rory Waterman
Inorganics 2016, 4(3), 26; https://doi.org/10.3390/inorganics4030026 - 15 Aug 2016
Cited by 7 | Viewed by 4429
Abstract
Zirconium-catalyzed alkene hydrophosphination and dehydrocoupling with an air-stable, fluorescent primary phosphine 8-[(4-phosphino)phenyl]-4,4-dimethyl-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene furnishes fluorescent phosphine products. Hydrophosphination of the fluorescent phosphine produces products with a complete selectivity for the secondary product. A key intermediate in catalysis, a zirconium phosphido compound, was isolated. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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5464 KiB  
Article
Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates
by Nerea Andino, Beñat Artetxe, Santiago Reinoso, Pablo Vitoria, Leire San Felices, Jose I. Martínez, Fernando López Arbeloa and Juan M. Gutiérrez-Zorrilla
Inorganics 2016, 4(2), 14; https://doi.org/10.3390/inorganics4020014 - 12 May 2016
Cited by 5 | Viewed by 6404
Abstract
New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [...] Read more.
New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)4]3[H(POC11H9)2(α-HBW11O39)] (TBA-1) and [N(C4H9)4]3[H(POC11H9)2(α-SiW11O39)] (TBA-2). Liquid-solution UV–Vis transmittance and solid-state diffuse reflectance spectroscopy studies reveal the presence of a new absorption band in the visible region, the charge transfer character of which has been further confirmed by time-dependent density functional theory (TD-DFT) calculations. The latter evidence that the charge transfer process is dominated by transitions from the highest occupied molecular orbital (HOMO), localized in the aromatic ring of the organic group, to the lowest unoccupied molecular orbital (LUMO), localized in the Keggin anion. Photoluminescence studies show that the fluorescent properties of the 1-naphthylmethylphosphonate group are quenched upon its incorporation into the inorganic oxo-tungstate skeleton. The solution stability of the hybrid clusters has been evaluated by a combination of 1H-, 13C- and 31P-Nuclear Magnetic Resonance spectroscopy and Electrospray Ionization-Mass Spectrometry. The hybrid polyanion [H(POC11H9)2(α-HBW11O39)]3− (1) herein constitutes the first structurally characterized organo-p-block containing borotungstate, and hence it confirms that this strategy for the organic functionalization of polyoxometalate clusters can be applied to new platforms belonging to the family of group-13 heteropolyoxotungstates. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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